WO2011125924A1 - 電線被覆材用組成物、絶縁電線及びワイヤーハーネス - Google Patents

電線被覆材用組成物、絶縁電線及びワイヤーハーネス Download PDF

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WO2011125924A1
WO2011125924A1 PCT/JP2011/058394 JP2011058394W WO2011125924A1 WO 2011125924 A1 WO2011125924 A1 WO 2011125924A1 JP 2011058394 W JP2011058394 W JP 2011058394W WO 2011125924 A1 WO2011125924 A1 WO 2011125924A1
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mass
wire
parts
composition
functional group
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PCT/JP2011/058394
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English (en)
French (fr)
Japanese (ja)
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達也 嶋田
坂本　幸弘
佐藤　正史
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株式会社オートネットワーク技術研究所
住友電装株式会社
住友電気工業株式会社
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Application filed by 株式会社オートネットワーク技術研究所, 住友電装株式会社, 住友電気工業株式会社 filed Critical 株式会社オートネットワーク技術研究所
Priority to DE112011101191.1T priority Critical patent/DE112011101191B4/de
Priority to US13/636,221 priority patent/US9305678B2/en
Priority to CN201180018045.6A priority patent/CN102884122B/zh
Publication of WO2011125924A1 publication Critical patent/WO2011125924A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C08K2003/3036—Sulfides of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/378—Thiols containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

  • the present invention relates to a composition for a wire covering material, an insulated wire, and a wire harness, and more specifically, a composition for a wire covering material having flame retardancy suitable as a covering material for an automotive insulated wire or the like that requires high heat resistance. Thing, an insulated wire using this, and a wire harness.
  • vinyl chloride resin cross-linked electric wires and polyolefin cross-linked electric wires have been used as electric wires used in places that generate high temperatures such as automobile wire harnesses.
  • These crosslinking methods for the crosslinked wires are generally carried out in a water vapor atmosphere or the like using electron beam irradiation or a silane functional group as a coating material.
  • Patent Document 1 as a composition used for a wire coating material, 100 parts by mass of at least one polymer selected from the group consisting of a thermoplastic resin, rubber, and a thermoplastic elastomer, an organic peroxide of 0.01
  • a resin composition for mixing with a silane-crosslinkable polyolefin comprising -0.6 parts by mass, silanol condensation catalyst 0.05-0.5 parts by mass, and magnesium hydroxide 100-300 parts by mass.
  • an inorganic hydroxide such as magnesium hydroxide is used as a flame retardant as in Patent Document 1 in order to impart flame retardancy to an electric wire.
  • an inorganic hydroxide such as magnesium hydroxide
  • a large amount of a flame retardant such as an inorganic hydroxide is added, the mechanical strength of the resin coating is lowered.
  • An electric wire in which an insulating film is formed using a composition made of a non-crosslinked resin instead of a crosslinked resin is superior in flexibility and can be provided at a lower cost than those using a crosslinked resin.
  • an insulated wire using a flame retardant resin composition made of a non-crosslinked material as an insulating film has a problem that its characteristics such as heat resistance and wear resistance are insufficient.
  • the present invention has been made in view of the above circumstances, and a problem to be solved by the present invention is to use a non-crosslinked material and to have an electric wire having excellent flexibility, heat resistance, and wear resistance. It is providing the composition for coating
  • the composition for a wire coating material is: (A) polypropylene, (B) polyolefin elastomer, (C) Brominated flame retardant, (D) antimony trioxide, (E) magnesium hydroxide, (F) (F1) zinc sulfide, or (F2) zinc oxide and (F3) mercaptobenzimidazole, (G)
  • the gist is to contain a hindered phenol-based antioxidant.
  • the gist of the insulated wire according to the present invention is an insulated wire having an insulating coating made of the above-described composition for wire covering material, having an insulation thickness of 0.5 mm or less and an outer diameter of 4 mm or less.
  • the gist of the wire harness according to the present invention is to have the above insulated wire.
  • composition for a wire covering material is: (A) polypropylene, (B) polyolefin elastomer, (C) Brominated flame retardant, (D) antimony trioxide, (E) magnesium hydroxide, (F) (F1) zinc sulfide, or (F2) zinc oxide and (F3) mercaptobenzimidazole, (G) a hindered phenolic antioxidant, Is included. Therefore, even if it is a non-crosslinked resin film, a film excellent in flame retardancy, heat resistance, abrasion resistance, flexibility and the like can be obtained.
  • the formed coating does not require a large amount of filler such as magnesium hydroxide as a flame retardant, there is no possibility that the heat resistance inherent to the resin is lowered by the large amount of filler added.
  • An insulated wire according to the present invention is an insulated wire having the above-described composition for a wire coating material, and has an insulation thickness of 0.5 mm or less and an outer diameter of 4 mm or less, so that it has flame resistance, heat resistance, and wear resistance. It is excellent in flexibility and can be provided at low cost.
  • the wire harness according to the present invention has the above insulated wire, it is excellent in flame retardancy, heat resistance, wear resistance, flexibility, and the like, and can be provided at low cost.
  • FIG. 1A and 1B are explanatory views showing an outline of the flexibility test apparatus, in which FIG. 1A shows a state before an electric wire is attached, and FIG. 1B shows a state where the electric wire is attached.
  • composition for wire covering materials according to the present invention can be composed of, for example, the following components.
  • A Polypropylene
  • B Polyolefin elastomer
  • C Brominated flame retardant
  • D Antimony trioxide
  • E Magnesium hydroxide
  • F Zinc sulfide or (F2) Zinc oxide and
  • G Mercaptobenzimidazole
  • H hindered phenol antioxidant
  • H1 a functional group-modified styrene elastomer modified with a compound having a functional group
  • H2 a functional group-modified polyolefin modified with a compound having a functional group
  • I Unmodified styrenic elastomer
  • Copper damage inhibitor and the like Copper damage inhibitor and the like.
  • polypropylene is used as a base resin.
  • Polypropylene has improved heat resistance but lowers the flexibility of the coating compared to polyethylene. In particular, when the electric wire has a small diameter, flexibility does not matter even if polypropylene is used. As a result, a flame retardant resin film excellent in heat resistance can be obtained even with a non-crosslinked resin.
  • Polypropylene is preferably an unmodified resin that has not been modified with a functional group, a silane coupling agent, or the like.
  • the (A) polypropylene may be a propylene homopolymer, a block polypropylene or a random polypropylene which is a copolymer with ethylene, butylene or the like.
  • Polypropylene preferably contains 50% by mass or more of a propylene component.
  • limiting in the molecular structure of a polypropylene You may use a syndiotactic polypropylene, an isotactic polypropylene, and an atactic polypropylene.
  • the flexural modulus of the (A) polypropylene is preferably in the range of 800 to 2000 MPa, more preferably in the range of 1000 to 1500 MPa.
  • wear resistance can be imparted to the electric wire.
  • the flexural modulus increases, the flexibility decreases.
  • the balance between wear resistance and flexibility is good.
  • the MFR (melt flow rate) at 230 ° C. of the (A) polypropylene is preferably in the range of 0.5 to 5 g / 10 min, more preferably in the range of 0.5 to 3 g / 10 min.
  • the MFR of polypropylene is reduced, the dispersibility of fillers such as flame retardant components may be reduced, which may cause generation of aggregated foreign matters. If the MFR of polypropylene becomes too large, mechanical properties such as wear resistance may be deteriorated.
  • the MFR of polypropylene is within the above range, a material having sufficient fluidity at the time of mixing the materials, without impairing productivity, and having good mechanical properties can be obtained. In the present invention, all MFR values are measured at 230 ° C.
  • the (B) polyolefin elastomer is used for imparting flexibility to the coating.
  • Polyolefin elastomers include olefinic thermoplastic elastomers (TPO), ethylene-propylene copolymers (EPM, EPR), ethylene propylene-diene copolymers (EPDM, EPT), butadiene rubber (BR), hydrogenated Butadiene rubber (EBR) can be used.
  • TPO olefinic thermoplastic elastomers
  • EPM ethylene-propylene copolymers
  • EPDM ethylene propylene-diene copolymers
  • BR butadiene rubber
  • EBR hydrogenated Butadiene rubber
  • the flexural modulus of the polyolefin elastomer is preferably less than 300 MPa, more preferably less than 250 MPa. When the flexural modulus of the polyolefin elastomer is reduced, the flexibility is improved.
  • the MFR of the (B) polyolefin elastomer is preferably 1 g / 10 min or more.
  • the upper limit of MFR of the polyolefin elastomer is preferably 10 g / 10 min or less.
  • the wire covering material composition according to the present invention includes (H) a functional group-modified resin, (I) an unmodified styrenic elastomer, and the like. Other resins may be added.
  • the (H) functional group-modified resin any one of (H1) functional group-modified styrene-based elastomer, (H2) functional group-modified polyolefin, or the above (H1) + (H2) can be used.
  • (H1) Functional group-modified styrene elastomer or (H2) functional group-modified polyolefin is a styrene elastomer (sometimes called styrene thermoplastic elastomer or styrene block copolymer) or a compound having a functional group with respect to polyolefin. It is a resin in which a functional group is introduced.
  • the (H) functional group-modified resin is added to the resin composition, the dispersibility of the filler, which is a flame retardant, is improved, and the physical properties of the coating are improved.
  • the mixing property of the coating material is improved by the addition of the functional group-modified resin, there are no irregularities and irregularities on the surface of the electric wire, the appearance is improved, and the electric wire extrusion may be improved.
  • Examples of the functional group of the functional group-modified resin include a carboxyl group, an acid anhydride group, an amino group, an epoxy group, a silane group, and a hydroxyl group.
  • a carboxyl group, an acid anhydride group, an amino group, an epoxy group, and the like are preferable from the viewpoint of mainly good adhesion to an inorganic filler.
  • the styrene elastomer used for the (H1) functional group-modified styrene elastomer uses polystyrene (PS) for the hard segment and polybutadiene (BR), polyisoprene (IR), hydrogenated (or partially hydrogenated) for the soft segment.
  • a block copolymer is formed using BR (EB), hydrogenation (or partial hydrogenation) IR (EP), and the like.
  • -Styrene copolymer modified butadiene rubber having a core-shell structure, styrene-isoprene block copolymer, hydrogenated or partially hydrogenated derivative styrene-ethylene-isoprene-styrene copolymer, maleic anhydride modified styrene- Examples thereof include an ethylene-isoprene-styrene copolymer and a modified isoprene rubber having a core-shell structure.
  • the polymer copolymerized with styrene may be a combination of butadiene, isoprene, etc., or a hydrogenated or partially hydrogenated derivative thereof.
  • Styrenic elastomers may be used alone or in combination.
  • polystyrene resin examples include, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ultra-low Polyethylene such as density polyethylene (VLDPE), polypropylene, homopolymers of other olefins, ethylene- ⁇ olefin copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-methacrylate esters Propylene copolymers such as ethylene copolymers such as polymers, propylene- ⁇ olefin copolymers, propylene-vinyl acetate copolymers, propylene-acrylic acid ester copolymers, propylene-methacrylic acid ester copolymers , Ethylene elastomer Examples include elastomers based on olefins such as tomer (HDPE), medium density polyethylene (MDPE), low density polyethylene
  • polystyrene resin examples include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and ethylene-methacrylic acid copolymer.
  • the (H1) functional group-modified styrene elastomer and (H2) functional group-modified polyolefin may contain one or more functional groups.
  • One or two or more of the same or different resins modified with different functional groups and different resins modified with the same functional group may be contained.
  • the functional group amount of the functional group-modified resin is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyolefin.
  • the functional group amount of the functional group-modified resin exceeds 10 parts by mass, the covering strip property at the time of processing the end of the electric wire may be deteriorated.
  • the functional group amount of the functional group-modified resin is less than 0.5 parts by mass, the modification effect by the functional group may be insufficient.
  • Specific examples of the method for modifying the polyolefin with a functional group include a method in which a compound having a functional group is graft-polymerized to the polyolefin, or a compound having a functional group and an olefin monomer are copolymerized to obtain an olefin copolymer. Methods and the like.
  • Specific examples of the compound that introduces a carboxyl group or an acid anhydride group as a functional group include ⁇ , ⁇ -unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, or anhydrides thereof.
  • Examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinyl acetic acid and pentenoic acid.
  • Specific examples of compounds that introduce amino groups as functional groups include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutylaminoethyl.
  • Specific examples of compounds that introduce an epoxy group as a functional group include glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl.
  • Glycidyl esters such as esters, ⁇ -chloroacrylic acid, maleic acid, crotonic acid, fumaric acid, glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, p-glycidyl Examples include styrene.
  • (I) unmodified styrene elastomer may be added as a resin component in addition to the above resin.
  • the unmodified styrene-based elastomer the styrene-based elastomer before modification described in the above functional group-modified styrene elastomer can be used.
  • the proportion of the resin component comprising (A) polypropylene and (B) polyolefin elastomer in the entire composition is usually 35% by mass or more, preferably 40% by mass. % Or more, and more preferably 45% by mass or more.
  • the total of (A) polypropylene and (B) polyolefin elastomer is preferably 70% by mass or more in the resin component, More preferably, it is 80 mass% or more.
  • the mixing ratio of (A) polypropylene and (B) polyolefin elastomer is within the above range, there is an advantage that mechanical properties such as wear resistance are improved.
  • the addition amount of other resin components other than the above (A) and (B) such as the above-mentioned (H) functional group-modified resin and (I) unmodified styrenic elastomer in the wire coating material composition is the above (A).
  • the amount is preferably in the range of 5 to 40 parts by mass, more preferably in the range of 5 to 20 parts by mass with respect to 100 parts by mass of the component (B).
  • the content of these other resin components is in the above range, the wire physical properties such as tensile properties are good, and the melting properties with the base material and the like are not deteriorated, and the material mixing is good.
  • the composition for a wire covering material according to the present invention uses (C) a brominated flame retardant, (D) antimony trioxide, and (E) magnesium hydroxide as a flame retardant.
  • D By using antimony trioxide in combination with (C) a brominated flame retardant, a flame retardant synergistic effect is obtained.
  • E The addition of magnesium hydroxide can impart a flame retardant effect and adjust the hardness of the coating. In addition, since magnesium hydroxide alone is not used as the flame retardant in the present invention, the amount of magnesium hydroxide added can be reduced as compared with the case where magnesium hydroxide is used alone as the flame retardant.
  • Brominated flame retardants specifically include ethylene bis (pentabromobenzene) [alias: bis (pentabromophenyl) ethane], tetrabromobisphenol A (TBBA), hexabromocyclododecane (HBCD), bis (Tetrabromophthalimide) ethane, TBBA-carbonate oligomer, TBBA-epoxy oligomer, brominated polystyrene, TBBA-bis (dibromopropyl ether), poly (dibromopropyl ether), hexabromobenzene (HBB) and the like.
  • pentabromobenzene [alias: bis (pentabromophenyl) ethane], tetrabromobisphenol A (TBBA), hexabromocyclododecane (HBCD), bis (Tetrabromophthalimide) ethane, TBBA-carbonate oli
  • a brominated flame retardant having a relatively high melting point has good flame retardancy, and specifically has a melting point of 200 ° C. or higher.
  • Preferred brominated flame retardants include ethylene bis (pentabromobenzene), bis (tetrabromophthalimide) ethane, TBBA-bis (dibromopropyl ether) and the like. These brominated flame retardants have good compatibility with the flame retardant mechanism of the base resin and have a good flame retardant effect.
  • antimony trioxide having a purity of 99% or more.
  • Antimony trioxide is preferably obtained by pulverizing and atomizing antimony trioxide produced as a mineral because of its low cost and high purity.
  • the average particle diameter of antimony trioxide is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less. When the average particle size of antimony trioxide is increased, the interface strength with the resin may be reduced.
  • Antimony trioxide may be subjected to a surface treatment for the purpose of controlling the particle diameter or improving the interfacial strength with the resin.
  • the surface treatment agent include silane coupling agents, higher fatty acids, polyolefin waxes, and the like.
  • Magnesium hydroxide is synthesized using natural magnesium hydroxide derived from natural mineral obtained by pulverizing a mineral mainly composed of magnesium hydroxide, or Mg source (such as bittern) contained in seawater as a raw material. Synthetic magnesium hydroxide can be used.
  • the particle size of magnesium hydroxide is usually about 0.5 to 20 ⁇ m, preferably 0.5 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m. When the particle diameter of magnesium hydroxide exceeds 20 ⁇ m, the appearance of the electric wire may be deteriorated, and when it is less than 0.5 ⁇ m, secondary aggregation may occur and the electric wire characteristics may be deteriorated.
  • the natural magnesium hydroxide may be subjected to a surface treatment using one or more of the following surface treatment agents because the adhesion with the resin may be reduced due to the unevenness of the particle surface.
  • the surface treatment agent include silane coupling agents, titanate coupling agents, fatty acids, fatty acid salts, fatty acid ester compounds, and olefin waxes.
  • the addition amount of the surface salt treating agent is preferably 0.3 to 5% by mass with respect to the total amount with magnesium hydroxide.
  • the surface treatment method is not particularly limited, and various known treatment methods can be used. If the addition amount of the surface treatment agent is less than 0.5% by mass, there is no effect in improving the electric wire characteristics, and if it exceeds 5% by mass, the amount necessary for the surface treatment may be exceeded and the electric wire characteristics may be deteriorated.
  • the amount of flame retardant added is as follows.
  • the amount of the flame retardant added is within the above range, a sufficient flame retardant effect can be obtained, and the cost cannot be increased more than necessary, and the flame retardant and the cost can be excellently balanced.
  • (F) As an additive for improving heat resistance (F1) zinc sulfide, or (F2) zinc oxide and (F3) mercaptobenzimidazole are used. Even if either (F1) addition of zinc sulfide alone or (F2) zinc oxide and (F3) mercaptobenzimidazole are selected in combination, the same heat resistance effect is obtained.
  • Zinc oxide can be obtained, for example, by adding a reducing agent such as coke to zinc ore and oxidizing zinc vapor generated by firing with air, or using zinc sulfate or zinc chloride as the salt amount.
  • the manufacturing method of zinc oxide is not particularly limited, and may be manufactured by any method.
  • As for (F1) zinc sulfide those produced by known methods can be used.
  • the average particle diameter of zinc oxide or zinc sulfide is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less. When the average particle size of zinc oxide or zinc sulfide is reduced, the interfacial strength with the resin is improved and the dispersibility is also improved.
  • Examples of the (F3) mercaptobenzimidazole include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 4-mercaptomethylbenzimidazole, 5-mercaptomethylbenzimidazole, and zinc salts thereof.
  • Particularly preferred mercaptobenzimidazole is 2-mercaptobenzimidazole and its zinc salt because it has a high melting point and little sublimation during mixing, and is stable at high temperatures.
  • Mercaptobenzimidazole does not lose its effect even when used in combination with other additives.
  • the other additives include thiazole compounds, sulfenamide compounds, thiuram compounds, dithiocarbamate compounds, xanthate compounds, and the like. These may be contained alone or in combination of two or more.
  • sulfenamide-based compounds include N-cyclohexyl-2-benzthiazole sulfenamide, N-tert-butyl-2-benzthiazole sulfenamide, N-oxydiethylene-2-benzthiazole sulfenamide, N, Examples thereof include N-diisopropyl-2-benzthiazole sulfenamide, N, N′-dicyclohexyl-2-benzthiazole sulfenamide, and the like.
  • thiuram compounds include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, tetrakis (2-ethylhexyl) thiuram disulfide and the like.
  • dithiocarbamate compound examples include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, dibenzyldithiocarbamine Examples include zinc acid.
  • Examples of the xanthate-based compound include sodium isopropyl xanthate, zinc isopropyl xanthate, and zinc butyl xanthate.
  • Hindered phenol antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-dithione).
  • Preferred hindered phenol antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert. -Butyl-4-hydroxyphenyl) propionate] and the like.
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
  • thiodiethylenebis 3- (3,5-di-tert. -Butyl-4-hydroxyphenyl) propionate
  • an amine copper damage inhibitor such as 3- (N-salicyloyl) amino-1,2,4-triazole is used. Heat resistance improves further by adding (J) copper damage inhibitor to a composition.
  • the addition amount of the copper damage inhibitor is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the resin component (A) polypropylene + (B) polyolefin elastomer.
  • additives used for general wire covering materials may be added to the wire covering material composition within a range that does not impair the wire characteristics.
  • the insulated wire according to the present invention has a wire covering material (sometimes referred to as an insulating coating) made of the above composition for a wire covering material on the outer periphery of a conductor.
  • Copper is generally used as the conductor, but metals such as aluminum and magnesium can be used in addition to copper. Moreover, you may contain another metal in copper. Other metals include iron, nickel, magnesium, silicon and the like, and other metals widely used as conductors may be added to copper or used alone.
  • a single wire may be used as the conductor, or a plurality of single wires may be twisted together. At this time, twisting and compressing is desirable because the diameter can be reduced.
  • the insulated wire according to the present invention is a thin wire having an outer diameter of 4 mm or less. Moreover, the thickness (insulation thickness) of the insulation film of an insulated wire is 0.5 mm or less. In the insulated wire, the insulating coating may be either a single layer or a plurality of layers.
  • the composition for wire covering material composed of the above components may be heated and kneaded, and then the obtained kneaded product may be extrusion coated on the outer periphery of the conductor to form an insulating coating.
  • the insulated wire of the present invention is used in a state where the resin is not cross-linked. Since the insulating coating is composed of non-crosslinked resin, there are the following advantages. Since the resin becomes hard in the cross-linked electric wire, the flexibility is impaired, but in the case of a non-cross-linked resin, the flexibility is obtained.
  • the non-crosslinked resin can be easily regenerated when recycling the electric wire or the like, but in the case of the crosslinked resin, it is difficult to recycle the resin.
  • facilities such as an electron beam irradiation device and a steam heating device are required, and the number of crosslinking treatment steps increases.
  • Non-bridging wires do not require any such equipment and do not require a crosslinking step. Therefore, the non-crosslinked electric wire can be provided at a lower cost than the crosslinked electric wire, and the productivity is high.
  • a conventional kneader such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin screw extruder, or a roll can be used.
  • the wire harness which concerns on this invention has the insulated wire mentioned above.
  • covered with the wire harness protective material can be illustrated.
  • the number of wires included in the single wire bundle and the mixed wire bundle can be arbitrarily determined and is not particularly limited.
  • the structure of other insulated wires included is not particularly limited.
  • the wire covering material may have a single layer structure or a two layer structure.
  • covering material of another insulated wire is not specifically limited, either.
  • the wire harness protective material has a role of covering the outer periphery of the wire bundle and protecting the inner wire bundle from the external environment or the like, and an adhesive is provided on at least one surface of the tape-shaped base material. Examples thereof include those coated and those having a substrate formed in a tube shape, a sheet shape, or the like. These can be appropriately selected and used according to the application.
  • the base material constituting the wire harness protective material for example, various non-halogen flame retardant resin compositions, vinyl chloride resin compositions, or halogen resin compositions other than the vinyl chloride resin composition, etc. Can be mentioned.
  • test materials and manufacturers The test materials used in the present examples and comparative examples are shown together with the manufacturer, product name, and the like. For polypropylene and polyolefin elastomer, the elastic modulus and MFR are shown.
  • PP1 “Novatech FY6C” manufactured by Nippon Polypro Co., Ltd., elastic modulus 2100 MPa, MFR 2.4 g / 10 min [2]
  • PP2 “Novatec EC9” manufactured by Nippon Polypro Co., Ltd., elastic modulus of 1200 MPa, MFR 0.5 g / 10 min [3]
  • PP3 “WP712” manufactured by Sumitomo Chemical Co., Ltd., elastic modulus 750 MPa, MFR 15 g / 10 min [4] PP4: manufactured by basel, “EP-310D”, elastic modulus 1200 MPa, MFR 0.5 g / 10 min
  • Olefin elastomer 1 manufactured by basel, “adflex Q100F”, elastic modulus 80 MPa, MFR 0.6 g / 10 min [6] Olefin elastomer 2: “adflex Q300F” manufactured by basel, elastic modulus 330 MPa, MFR 0.8 g / 10 min [7] Olefin elastomer 3: “ESPOLEX 821” manufactured by Sumitomo Chemical Co., Ltd., elastic modulus: 62 MPa, MFR: 1.2 g / 10 min [8] Olefin elastomer 4: manufactured by Sumitomo Chemical Co., Ltd., “ESPOLEX 817”, elastic modulus 360 MPa, MFR 1.1 g / 10 min
  • Styrenic elastomer 1 “Tuftec H1041” manufactured by Asahi Kasei Chemicals Corporation
  • Styrene elastomer 2 “Septon 2002” manufactured by Kuraray Co., Ltd.
  • Brominated flame retardant 1 Ethylene bis (pentabromobenzene): “SAYTEX 8010” manufactured by Albemarle
  • Brominated flame retardant 2 TBBA-bis (dibromopropyl ether): “FCP-680” manufactured by Suzuhiro Chemical Co., Ltd.
  • Brominated flame retardant 3 Tetrabromobisphenol A: “SAYTEXCP2000” manufactured by Albemarle
  • Antimony trioxide manufactured by Yamanaka Sangyo Co., Ltd., “Antimony trioxide MSW grade”
  • Hindered phenolic antioxidant 1 “Irganox 1010” manufactured by Ciba Japan
  • Hindered phenolic antioxidant 2 “Irganox 1330” manufactured by Ciba Japan
  • Zinc oxide manufactured by Hakusuitec Co., Ltd.
  • Zinc sulfide “SachtolithHD-S” manufactured by Sachtleben Chemie GmbH
  • Mercaptobenzimidazole 1 “ANTAGE MB” manufactured by Kawaguchi Chemical Industry Co., Ltd.
  • Mercaptobenzimidazole 2 “Nokutarak MB” manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • the tensile elongation was measured according to the tensile test of JIS D608. In other words, an insulated wire is cut to a length of 100 mm, a conductor is removed to form a tubular test piece made of only an insulation coating material, and both ends of the test piece are attached to a chuck of a tensile tester at room temperature of 23 ⁇ 5 ° C. After that, the sample was pulled at a pulling speed of 200 mm / min, and the load and elongation at break of the test piece were measured. A tensile elongation of 125% or more was evaluated as “good”, and 300% or more was evaluated as “good”.
  • the tensile force (F) required to pass the electric wire through the test apparatus was obtained from the following equation.
  • the tensile force F is a flexibility index indicating flexibility. The smaller this value, the higher the flexibility. If the tensile force F is 3.5 N or less, the pass is “good”, if it is 2.3 N or less, it is “good”, and if it is more than 3.5 N, the fail is “x”.
  • F F1-F2-F3
  • test solutions immerse 8 test pieces in the test solution, place them in a constant temperature bath at 20 ⁇ 3 ° C., and remove them after 240 hours.
  • the remaining six test pieces were immersed in the test solution in the same manner as in the first case, placed in a thermostatic bath again, taken out after 240 hours, and subjected to a winding test of two test pieces (after 480 hours).
  • the remaining four test pieces were immersed in the test solution in the same manner as in the first case, placed in a thermostatic bath, taken out after 240 hours, and subjected to a winding test (720 hours later) of the two test pieces.
  • the remaining two test pieces were immersed in a test solution as in the first case, put in a thermostatic bath, taken out after 240 hours, and subjected to a winding test (after 960 hours).
  • test solution of group 2 After immersing two test pieces in each test solution as in the case of group 1, place them in a constant temperature bath at 20 ⁇ 3 ° C. and hold for 360 hours, and then wind test Went.
  • Test solution The composition% of the test solution is volume% unless otherwise specified.
  • the winding test after taking out from the thermostat was performed as follows. A test piece which had been put in a thermostatic chamber for a predetermined time was taken out and left at room temperature (23 ° C. ⁇ 5 ° C.) for 30 minutes, and then a winding test was performed at room temperature. In the winding test, the central portion of the test piece was used, and the state of the insulating coating was visually observed after winding around a mandrel ( ⁇ 6). As a result, if the conductor was exposed, a withstand voltage test was conducted for 1 minute (1 kv), and the case where there was no dielectric breakdown was accepted and the others were rejected.
  • the insulated wire was subjected to an aging test of 100 ° C. ⁇ 3000 hours and 125 ° C. ⁇ 3000 hours, and then a withstand voltage test of 1 kv ⁇ 1 min was performed. As a result, the case where it was able to withstand 100 ° C. was judged as “good”, the case where it was able to withstand 125 ° C. was judged as “good”, and the case where it was not able to withstand 100 ° C. did.
  • Wire harness form that is, the outer periphery of a mixed wire bundle in which insulated wire test pieces and vinyl chloride-based insulated wires are mixed in an arbitrary number, wrapped with a tape with a vinyl chloride-based adhesive at 150 ° C for 240 hours After aging, one arbitrary insulated wire test piece was taken out from the mixed wire bundle, self-diameter winding was performed, and the appearance of the test piece was visually observed. As a result, the case where the conductor was not exposed from the insulating coating of the insulated wire was judged as “good”, and the case where the conductor was exposed was judged as “bad”.
  • Comparative Example 1 does not contain a brominated flame retardant as compared with Example 1. Therefore, it is inferior to flame retardancy.
  • Comparative Example 2 does not contain magnesium hydroxide. Therefore, it is inferior to flame retardancy.
  • Comparative Example 3 does not contain an olefin elastomer. Therefore, it is inferior in flexibility.
  • Comparative Example 4 does not contain polypropylene. Therefore, it is inferior in heat resistance, abrasion resistance, productivity, chemical resistance and the like.
  • Comparative Example 5 does not contain zinc sulfide, zinc oxide, or mercaptobenzimidazole. Therefore, it is inferior in heat resistance and cooperation.

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PCT/JP2011/058394 2010-04-05 2011-04-01 電線被覆材用組成物、絶縁電線及びワイヤーハーネス WO2011125924A1 (ja)

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US13/636,221 US9305678B2 (en) 2010-04-05 2011-04-01 Composition for wire coating member, insulated wire, and wiring harness
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CN104710675A (zh) * 2012-11-20 2015-06-17 日立金属株式会社 非卤素耐热老化性阻燃树脂组合物、使用其的电线及电缆
CN104903978A (zh) * 2013-01-07 2015-09-09 矢崎总业株式会社 耐热交联电线
WO2017017875A1 (ja) * 2015-07-29 2017-02-02 出光ライオンコンポジット株式会社 高反射難燃熱可塑性樹脂組成物、成形体及び照明機器用反射板
CN107735445A (zh) * 2015-07-29 2018-02-23 出光狮王塑料株式会社 高反射阻燃热塑性树脂组合物、成形体和照明机器用反射板
EP3772069A1 (de) * 2019-07-30 2021-02-03 Nexans Elektrisches kabel mit verbesserter wärmeleitfähigkeit
FR3099631A1 (fr) * 2019-07-30 2021-02-05 Nexans Câble électrique présentant une conductivité thermique améliorée
WO2022190850A1 (ja) * 2021-03-08 2022-09-15 株式会社オートネットワーク技術研究所 通信用電線、ワイヤーハーネス、および通信用電線の製造方法

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DE112011101191B4 (de) 2018-01-11
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